Facile Obtainment of Fluorescent PEG Hydrogels Bearing Pyrene Groups by Frontal Polymerization

Frontal polymerization (FP) was used to prepare poly(ethylene glycol) methyl ether acrylate (PEGMA) fluorescent polymer hydrogels containing pyrenebutyl pendant groups as fluorescent probes. The polymerization procedure was carried out under solvent-free conditions, with different molar quantities of pyrenebutyl methyl ether methacrylate (PybuMA) and PEGMA, in the presence of tricaprylmethylammonium (Aliquat 336®) persulfate as a radical initiator. The obtained PEGPy hydrogels were characterized by FT-IR spectroscopy, confirming the effective incorporation of the PybuMA monomer into the polymer backbone. The thermal properties of the hydrogels were determined using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). After immersing the hydrogels in deionized water at 25 °C and pH = 7, their swelling behavior was investigated by mass gain at different pH and temperature values. The introduction of PybuMA comonomer into the hydrogel resulted in a decreased swelling ability due to the hydrophobicity of PybuMA. The optical properties of PEGPy were determined by UV-visible absorption and fluorescence spectroscopies. Both monomer and excimer emission bands were observed at 379–397 and 486 nm, respectively, and the fluorescence spectra of the PEGPy hydrogel series were recorded in different solvents to explore the coexistence of monomer and excimer emissions

Experimental and theoretical study of the role of CH/pi interactions in the aminolysis reaction of acetyl galactoside

9 p.-8 fig.-6 tab.Molecular recognition of saccharides is a growing field, which has many implications in cancer therapy, drug discovery, and cellular communication among others. The participation of CH/pi interactions in this event is well known. Nevertheless, the intrinsic role of CH/pi for modulating chemical reactions is still far from being applicable. In this experimental and computational work we have evaluated the participation of CH/pi interactions in the aminolysis reaction of acetyl galactoside promoted with different 6-substituted 2(1H)-pyridones. Two features have been incorporated to the promoter molecular structure, on one end the promoting pyridone group and on the other end the recognition moiety, joined together by an alkyne spacer. The small increment in the observed pseudo-first-order rate constant values (kobs) was related to the stability of the transition state provided by noncovalent interactions, including CH/pi interactions. A longer alkyne spacer was necessary to improve the molecular recognition of the galactoside substrate. The trend of the calculated activation energy values (DeltaERTS) was in good accordance with the experimental rate constant values.We thank CONACyT (grants 165614 and 284923) and DGAPAUNAM (grant IN-209416) for financial support. We thank DGTICUNAM,for supercomputer resources (grant SC14-1-I-70). F C-G is grateful to CONACyT for the scholarship granted number 256121.Peer reviewe

Synthesis of β-Cyclodextrin-Decorated Dendritic Compounds Based on EDTA Core: A New Class of PAMAM Dendrimer Analogs

In this work, two dendritic molecules containing an ethylenediaminetetraacetic acid (EDTA) core decorated with two and four β-cyclodextrin (βCD) units were synthesized and fully characterized. Copper(I)-catalyzed alkyne–azide cycloaddition (CuAAC) click chemistry under microwave irradiation was used to obtain the target compounds with yields up to 99%. The classical ethylenediamine (EDA) core present in PAMAM dendrimers was replaced by an EDTA core, obtaining platforms that increase the water solubility at least 80 times compared with native βCD. The synthetic methodology presented here represents a convenient alternative for the rapid and efficient construction of PAMAM analogs. These molecules are envisaged for future applications as drug carriers